scholarly journals Thermodynamics of ester and orthoester formation from trifluoroacetic acid

1976 ◽  
Vol 54 (2) ◽  
pp. 202-209 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Equilibrium Constant ◽  
Trifluoroacetic Acid ◽  
Sodium Methoxide ◽  
Standard Free Energy ◽  
Steric Effects ◽  
Addition Reactions ◽  
Free Energies ◽  
Acetic Acids

The equilibrium constant for the addition of sodium methoxide to methyl trifluoroacetate, in methanol as solvent, has been measured by 19F nmr, and is 7 M−1. From this was calculated an equilibrium constant, 2 × 10−4 M−1, for addition of methanol to the ester. The equilibrium constant for formation of methyl trifluoroacetate in aqueous solutions is 0.06 M−1. These results, with literature data, permit calculation of the free energies of formation in aqueous solution of orthotrifluoroacetic acid and its mono-, di-, and trimethyl esters. These in turn permit calculation of the standard free energy changes for addition of water and methanol to trifluoroacetic acid and its methyl ester. These combined with the analogous values for formic and acetic acids permit evaluation of ρ* values for these addition reactions. Linear plots are obtained if correction is made for steric effects, and the ρ* values are somewhat larger, 2.1–2.9, than was observed for the analogous carbonyl addition reactions.

scholarly journals Carbonyl Addition Reactions: Factors Affecting the Hydrate–Hemiacetal and Hemiacetal–Acetal Equilibrium Constants

1975 ◽  
Vol 53 (6) ◽  
pp. 898-906 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Carbonyl Compounds ◽  
Equilibrium Constants ◽  
Substituent Effects ◽  
Steric Effects ◽  
Addition Reactions ◽  
Free Energies ◽  
Electronic Effects ◽  
Factors Affecting ◽  
Analogous Formula

Equilibrium constants for hydrate–hemiacetal interconversion in aqueous solution at 25° have been measured for four fluorinated carbonyl compounds: compound, alcohol, K4 (M−1): CF3CHO, C2H5OH, 2.3; CF3COCH3, CH3OH, 1.0; CF3COPh, CH3OH, 3.5; CF3COCF3, CH3OH, 0.14. These values, combined with values from the literature, permit an examination of substituent effects upon the equilibrium constant for[Formula: see text]The free energy change for this process, corrected for symmetry and steric effects, follows the equation[Formula: see text]Thus electronic effects upon this equilibrium are generally small and in fact are often smaller than steric effects.This analysis permits and justifies the calculation of free energies of formation of [Formula: see text] compounds from the (more generally measurable) free energies of formation of the analogous [Formula: see text] compounds.

Chemical equilibrium and chemical kinetics

2018 ◽  
Author(s):  
Dennis Sherwood ◽  
Paul Dalby
Keyword(s):  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Chemical Kinetics ◽  
Chemical Equilibrium ◽  
First Principles ◽  
Effect Of Temperature ◽  
Total System ◽  
Free Energies

Building on the previous chapter, this chapter examines gas phase chemical equilibrium, and the equilibrium constant. This chapter takes a rigorous, yet very clear, ‘first principles’ approach, expressing the total Gibbs free energy of a reaction mixture at any time as the sum of the instantaneous Gibbs free energies of each component, as expressed in terms of the extent-of-reaction. The equilibrium reaction mixture is then defined as the point at which the total system Gibbs free energy is a minimum, from which concepts such as the equilibrium constant emerge. The chapter also explores the temperature dependence of equilibrium, this being one example of Le Chatelier’s principle. Finally, the chapter links thermodynamics to chemical kinetics by showing how the equilibrium constant is the ratio of the forward and backward rate constants. We also introduce the Arrhenius equation, closing with a discussion of the overall effect of temperature on chemical equilibrium.

A QM/MM study combined with the theory of energy representation: Solvation free energies for anti/syn acetic acids in aqueous solution

2006 ◽  
Vol 419 (1-3) ◽  
pp. 240-244 ◽  
Author(s):  
Takumi Hori ◽  
Hideaki Takahashi ◽  
Masayoshi Nakano ◽  
Tomoshige Nitta ◽  
Weitao Yang
Keyword(s):  
Aqueous Solution ◽  
Free Energies ◽  
Solvation Free Energies ◽  
Acetic Acids

Design and Thermodynamic Analysis on One-Step Amination of Benzene to Aniline Systems

2012 ◽  
Vol 550-553 ◽  
pp. 2607-2611
Author(s):  
Chun Hua Yang ◽  
Gang Chen ◽  
Long Zhang
Keyword(s):  
Hydrogen Peroxide ◽  
Free Energy ◽  
Equilibrium Constant ◽  
Gibbs Free Energy ◽  
Driving Force ◽  
Theoretical Basis ◽  
Free Energies ◽  
One Step ◽  
The One ◽  
Further Development

Seven systems of one-step synthesis of aniline were designed, and it was determined which one could occur spontaneously through the calculation of Gibbs free energy of it. Among the seven systems, the Gibbs free energy of the one with ammonia as the aminating agent and hydrogen peroxide as the oxidant was the lowest, thus its process driving force was the largest, that is, .For this system just mentioned above, the standard Gibbs free energies, the equilibrium constant and the equilibrium conversions of benzene under different conditions were discussed ,which was expected to provide a theoretical basis for further development and application of the system.

The Construction of E–pH Diagrams

2010 ◽  
Author(s):  
George K. Schweitzer ◽  
Lester L. Pesterfield
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Standard Free Energy ◽  
Oxidation Number ◽  
Left Hand ◽  
Descriptive Chemistry ◽  
Ph Range

In order to construct an E–pH diagram one needs to follow eight basic steps: (1) Select the species of the element involved which contain one or more of the following entities: the element, oxygen, and hydrogen. This is best done by reading the descriptive chemistry of the element in a good inorganic text and identifying the species, both soluble and insoluble, which persist, at least for several minutes, in aqueous solution. (2) Starting at the lower left-hand corner of an E–pH framework, arrange the selected species in vertical order of increasing oxidation number of the element. Then, if there are different species with the same oxidation number, arrange them in horizontal order of decreasing protonation (increasing hydroxylation). If there is only one species of a given oxidation number, this species extends across the entire pH range for the purposes of diagram construction. (3) Draw in border lines between the species, that is, the lines representing the transformation of a species to another species. You will not know exactly where these lines occur but the approximate regions are sufficient for the purposes of diagram construction. (4) Write equations for the transformations that have been indicated. Some of them will involve electrons and therefore will be half-reactions. Such equations must always be written as reductions, that is, with the electrons on the left. In addition, no reaction should contain the OH− ion; only the H+ and/or HOH instead. (5) From appropriate tabulations, obtain the standard free energy values (ΔG° in kJ/mole) of every species in the equations. These ΔG° values are to be employed in the following relationship which applies to each of the above equations. . . . ΔG° (reaction) = ∑ΔG° (products) − ∑ΔG° (reactants) (6) . . . (6) The ΔG° (reaction) values for each equation are to be converted into E° values for those equations containing electrons and into K values for those equations which do not. This is done by use of the following expressions: . . . E° = ΔG° /−96.49n log K = ΔG° /−5.7 (7/8) . . . where n represents the number of electrons in an equation.

scholarly journals Biosorption of Pb(II) and Cu(II) from Aqueous Solution Using Chicken Feathers: Thermodynamics and Mass Balance Studies

2018 ◽  
pp. 1-9
Author(s):  
Salaudeen Abdulwasiu Olawale ◽  
Abdulrahman Wosilat Funke ◽  
Aliyu Haruna Dede ◽  
Yakubu Hajara
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Mass Balance ◽  
Thermodynamic Parameters ◽  
Adsorption Process ◽  
Standard Free Energy ◽  
Ftir Analysis ◽  
Substantial Variation ◽  
Chicken Feathers ◽  
Before And After

Thermodynamic and mass balance studies of Pb(II) and Cu(II) biosorption from aqueous solution using chicken feathers (CF) were carried out. Thermodynamic parameters such as standard free energy (ΔG0), enthalpy (ΔH0) and entropy (ΔS0) changes were calculated from the data obtained to predict the nature of adsorption by chicken feathers (CF). From the results, entropy changes were positive indicating an increase in disorderliness in the adsorption of Pb(II) and Cu(II) onto the chicken feathers (CF). The negative values of Gibbs free energy and positive values of enthalpy indicated that the adsorption process by CF was spontaneous and endothermic. Data obtained also showed that the percentage Cu(II) and Pb(II) released by CF after digestion at 25 mg/l were higher than those released at 100 mg/l. Finally, FTIR analysis confirmed the presence of carboxyl, hydroxyl, amino and sulphur containing functional groups on CF, with no substantial variation in the spectra obtained before and after adsorption indicating a possible re use of CF.

Tautomerization equilibria for phosphorous acid and its ethyl esters, free energies of formation of phosphorous and phosphonic acids and their ethyl esters, and pKa values for ionization of the P—H bond in phosphonic acid and phosphonic esters

1979 ◽  
Vol 57 (2) ◽  
pp. 236-239 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Equilibrium Constants ◽  
Phosphorous Acid ◽  
Triethyl Phosphite ◽  
Ethyl Esters ◽  
Free Energies ◽  
Phosphonic Acids ◽  
Hydroxy Compounds ◽  
Energy Relations

From data in the literature the free energies of formation in aqueous solution of triethyl phosphite and diethyl phosphonate can be calculated as −138.4 ± 1.7 and −165.1 ± 2.0 kcal mol−1, respectively. From these values, by application of free energy relations which we have published, the free energies of formation of the corresponding hydroxy compounds can be calculated and thence the equilibrium constants for tautomerization, which are 107.2, 108.7, and 1010.3 in favor of the tetracoordinate phosphonate tautomer for P(OEt)2OH, P(OEt)(OH)2, and P(OH)3, respectively. Using estimated pKa values for the tricoordinate phosphite species the tautomerization equilibria for the anions could also be calculated, as could the pKa values from the P—H bonds: 13, 26, and 38 for H—PO(OEt)2, H—PO2(OEt)−, and H—PO32−, respectively.

Conformational analysis in carbohydrate chemistry. I. Conformational free energies. The conformations and α : β ratios of aldopyranoses in aqueous solution

1968 ◽  
Vol 21 (11) ◽  
pp. 2737 ◽  
Author(s):  
SJ Angyal
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Conformational Analysis ◽  
Reasonable Agreement ◽  
Anomeric Effect ◽  
Interaction Energies ◽  
Free Energies ◽  
Carbohydrate Chemistry ◽  
Predominant Conformation

The relative free energies of the aldopyranoses in aqueous solution have been calculated, taking non-bonded interaction energies and the anomeric effect into account. It is shown that the calculated free-energy values correctly predict the predominant conformation of the α- and β-pyranose forms of each aldose. The α- to β-pyranose ratios of the aldoses in aqueous solution, calculated from these values, are in reasonable agreement with those determined experimentally.

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